Polymeric materials

ABSTRACT

NICKEL DI(HYDROCARBYL) DITHIOPHOSPHATES ARE INCLUDED AS STABILISING AGENTS IN POLYURETHANE COMPOSITIONS, PARTICULARLY FOAMS. THE SAID NICKEL COMPOUNDS MAY BE ADVANTAGEOUSLY USED IN CONJUNCTION WITH A NICKEL OR ZINC B-KETO-ENOLATE OR A ZINC DI(HYDROCARBYL DITHIOPHOSPHATE.

United States Patent 01 hce Patented Dec. 28, 1971 U.S. Cl. 260-45.75 N 3 Claims ABSTRACT OF THE DISCLOSURE Nickel di(hydrocarbyl) dithiophosphates are included as stabilising agents in polyurethane compositions, particularly foams. The said nickel compounds may be advantageously used in conjunction with a nickel or zinc ,B-keto-enolate or a zinc di(hydrocarbyl dithiophosphate.

This invention relates to polymeric materials and more particularly to polyurethane materials and methods for their stabilisation.

This application is a continuation of Ser. No. 647,602 filed June 21, 1967 and now abandoned.

It is already known to manufacture polyurethane materials in the form of foams, elastomers, fibres, coatings and adhesives by reacting organic polyisocyanates with organic polyhydroxy compounds. One disadvantage which has been encountered with these products is their tendency to discolour or degrade during preparation and use. The mechanism of this discoloration or degradation is not entirely clear and there may be several contributory causes. Thus, the discoloration or degradation which commonly occurs in the preparation of polyurethanes, especially foams, is undoubtedly associated with the elevated temperatures employed or attained in the highly exothermic reaction and is usually referred to as scorching. High temperature after-treatments also have a deleterious effect. Factors contributing to discoloration or degradation after preparation include the action of light, oxygen and contact with oxides of nitrogen. The total effect of these various influences may be that the polyurethane material develops in time an unattractive deep brown colour.

It has now been found that the discoloration and degradation of polyurethanes may be obviated or minimised wherein R and R are the same or different hydrocarbon radicals or derivatives thereof.

As examples of hydrocarbon radicals or derivatives thereof there may be mentioned alkyl (straight chain or branched), cycloalkyl, aryl, aralkyl radicals and alkyl radicals interrupted by one or more hetero atoms suchas O Alternatively the hydrocarbon radicals or derivatives thereof may together form an alkylene group, optionally substituted with hetero atoms such as O or S, which together with the remainder of the thio acid molecule forms a ring structure containing from 2 to 5 carbon atoms. Furthermore the radicals R and R' may each be bifunctional alkylene, arylene or alkylene interrupted by heteroatoms such as O or S which each link together two molecules of the thio acid giving rise to a polymeric dihydrocarbyl dithiophosphoric acid.

As examples of the hydrocarbon there may be mentioned ethyl, n-butyl, isopropyl, cyclohexyl, nonyl, phenyl, tolyl, 2-ethyl-hexyl and methoxyethyl.

As examples of alkylene or substituted alkylene radicals which together with the remainder of the thio acid molecule form a ring structure containing from 2 to 5 carbon atoms there may be mentioned ethylene, trimethylene and the radicals CH CH OCH CH and As examples of bifunctional radicals which link two thio acid radicals together there may be mentioned decamethylene, p-phenylene and polyoxyalkylene radicals such where n represents an integer greater than 1.

As examples of nickel di(hydrocarbyl) dithiophosphates suitable for use in the present invention there may be mentioned nickel dinonyldithiophosphate, nickel di-isopropyldithiophosphate, nickel diphenyldithiophosphate and the nickel salts of the di(hydrocarbyl) dithiophosphoric acids that are the reaction products of phosphorus pentasulphide with polyalkylene ethers of aliphatic monohydric alcohols, for example oxypropylated n-butanol or with polyalkylene plyols such as polypropylene glycol or oxypropylated glycerol.

*Mixtures of nickel di(hydrocarbyl) dithiophosphates may also be used in the present invention.

The stabilising effect of the nickel di(hydrocarbyl) dithiophosphates may be enhanced by using the said comcompounds in conjunction with a zinc di(hydrocarbyl) dithiophosphate or a zinc fi-keto-enolate. The protection against discoloration and degradation obtained by the use of such combinations is greater than the sum of the effects due to the individual agents used alone. A similar synergistic effect is obtained by the use of a nickel ,B-ketoenolate together with a zinc di(hydrocarbyl)dithiophosphate. A nickel [i-keto-enolate may also be used together with a nickel di(hydrocarbyl)dithiophosphate. Particularly effective combinations of agents are those containing approximately equal amounts of each agent although mixtures in other proportions are also very useful.

The zinc di(hydrocarbyl)dithiophosphates which may be used according to the present invention are exactly analogous to the nickel di(hydrocarbyl)dithiophosphates already described.

The nickel and zinc S-keto-enolates which may be used according to the present invention are compounds having the formula:

wherein M represents nickel or zinc and X, Y and Z independently represent hydrogen atoms or alkyl, cycloalkyl,

aralkyl, aryl, alkoxy or carboalkoxy groups. The aryl groups may optionally be substituted by hydroxyl, alkyl or alkoxy groups or halogen atoms. Alternatively X and Y together may form the residue of an aromatic system, for example phenyl or naphthyl which may optionally be further substituted by hydroxyl, alkyl or alkoxy groups or halogen atoms.

Examples of suitable fl-keto-enolates for use according to the present invention include the nickel and zinc complexes of acetylacetone, benzoylacetone, dibenZoylmethane, ethyl acetoacetate, diethyl malonate, salicylaldehyde, 2-hydroxybenzophenone and 2-hydroxy-4-alkoxybenzophenones. Mixtures of fi-keto-enolates may be used.

Suitable amounts of nickel di(hydrocarbyl)dithiophosphates to use according to the present invention are usually in the range of from 0.01% to 5%, and preferably from 0.1% to 2%, by weight based on the weight of the polyurethane. The said combinations of nickel and zinc compounds may be used in similar amounts.

The aforesaid stabilising agents may be incorporated into the polyurethane in any convenient manner. Thus the agents may be incorporated into a polyurethane elastomer by milling or may be added in solution form to a coating composition. It is usually preferred, however, to include the nickel di(hydrocarbyl)dithiophosphates or the aforesaid combinations of agents in the polyurethane-forming reaction mixture. This method of incorporation is particularly suitable where there is a risk of significant discoloration or degradation occurring during the formation of the polyurethane and is usually the most suitable method in the case of a foam.

Accordingly, the present invention provides a process for the manufacture of polyurethanes comprising reacting an organic polyisocyanate with an organic polyhydroxy compound in the presence of a nickel di(hydrocarbyl) dithiophosphate or a combination of nickel and zinc compounds selected from di(hydrocarbyl)dithiophosphates and ,B-keto-enolates wherein at least one of the compounds is a di(hydrocarbyl)dithiophosphate.

The starting materials to be used in the preparation of the polyurethanes may be those fully described in the prior art.

Examples of suitable organic polyisocyanates include aliphatic polyisocyanates such as hexamethylene diisocyanate and cycloaliphatic polyisocyanates such as dicyclohexylmethane diisocyanate but the invention is of particular value when aromatic polyisocyanates are used since the problems of discoloration are then much greater. Suitable aromatic polyisocyanates include tolylene-2,4,-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-4,4-diisocyanate, 3-methyldiphenylmethane-4,4-diisocyanate, mand p-phenylene diisocyanates, chorophenylene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 3,3-dimethyldiphenyl-4,4'-diisocyanate, diphenyl ether diisocyanate, 2,4,6-triisocyanatotoluene and 2,4,4-triisocyanatodiphenyl ether.

Examples of other suitable organic polyisocyanates comprise the reaction products of an excess of a diisocyanate with polyhydric alcohols such as trimethylolpropane and uretedione dimers and isocyanurate polymers of diisocyanates, for example of tolylene-2,4-diisocyanate. Mixtures of polyisocyanates may be used, for example mixtures of tolylene 2,4- and 2,6-diisocyanates or the mixtures of polyisocyanates obtained by the phosgenation of crude aromatic amine/formaldehyde reaction products.

Examples of suitable organic polyhydroxy compounds include hydroxyl group-containing polyesters, polyethers, polythioethers and polyacetals, i

Suitable hydroxyl group-containing polyesters may be made, for example, from polycarboxylic acids and polyhydric alcohols. Suitable polycarboxylic acids include succinic, glutaric, adipic, sebacic, phthalic, isophthalic, terephthalic and trimesic acids. Mixtures of acids may be used. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, decamethyene glycol, glycerol, trimethylolpropane and pentaerythritol. The polyesters may contain amide groups introduced by including a proportion of diamine or aminoalcohol in the polyester-forming reaction mixture. Suitable diamines and aminoalcohols include ethylene diamine, hexamethylene diamine, tolylene diamines and ethanolamines. The polyesters suitably have molecular weights between 300 and 6000.

Suitable hydroxyl group-containing polyethers may be prepared by the reaction of one or more alkylene oxides with a compound containing a plurality of active hydrogen atoms. Suitable alkylene oxides include ethylene oxide, epichlorohydrin, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and styrene oxide. Mixtures of two or more oxides may be used if desired, or, as a further variant, the active hydrogen-containing compound may be reacted with two or more alkylene oxides in successive stages, for example using propylene oxide in the first stage and ethylene oxide in the second. Compounds containing a plurality of active hydrogen atoms with which the alkylene oxides may be reacted include water, ammonia, hydrazine, cyanuric acid, phosphorous, phosphoric or phosphonic acids, polyhydroxy compounds, for example ethylene glycol, propylene glycol, diethylene glycol, glycerol, trirnethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, phenol-formaldehyde reaction products, resorcinol and phloroglucinol, aminoalcohols, for example monoethanolamine and diethanolamine, polyamines, for example ethylene diamine, hexamethylene diamine, tolylene diamines and diaminodiphenylmethanes and polycarboxylic acids, for example adipic acid, terephthalic acid and trimesic acid. The conditions for the reaction between the alkylene oxide and the active hydrogen containing compound may be those fully described in the prior art using, for example, basic catalysts such as potassium hydroxide or acidic catalysts such as boron trifiuoride. The reaction products may have molecular weights of between 300 and 8000 according to the amount of alkylene oxide reacted with the active hydrogen-containing compound.

The problems of discoloration are particularly great in the case of polyurethane foams, where the extremely rapid reaction causes particularly high temperatures to be reached within the foam. Discoloration or scorching is common, therefore, in polyurethane foams and is often especially marked at the centres of large blocks of foam where the heat generated is largely retained because of the insulating properties of the foams themselves. Discoloration with age also is particularly marked in the case of foams. The present invention is valuable as a means of reducing these undesirable effects.

Polyurethane foams may be prepared by reacting the organic polyisocyanate with the organic polyhydroxy compound in the presence of a blowing agent. Alternatively, a prepolymer may be formed by carrying out at least part of the reaction between the polyisocyanate and the polyhydroxy compound in one stage and then introducing the blowing agent subsequently.

Blowing agents which may be used in the process of the present invention include water which reacts with isocyanate groups forming carbon dioxide. Amounts of water which may suitably be used are from 0.5 to 10% based on the weight of polyhydroxy compound. Other blowing agents which may be used include inert low boiling-point liquids which vaporize under the influence of the exothermic reaction.

Suitable low boiling-point liquids are liquids that are inert towards the organic polyisocyanate and have boiling points not exceeding 75 C. at atmospheric pressure and preferably between -40 C. and 50 C. Examples of such liquids are halogenated hydrocarbons such as methylene chloride, vinylidene chloride and particular y As described fully in the prior art the general methods of preparation of polyurethanes may include the incorporation in the polyurethane-forming mixture of various additives such as surface-active agents, for example, oxyfluorinated hydrocarbons such as trichloromonofiuoroethylated fatty alkyl phenols, oxyethylated fatty alcohols, methane, dichlorodifluoromethane, dichloromonofluorosalts of sulphuric acid derivatives of high molecular methane, monochlorodifluoromethane, dichlorotetraweight organic compounds and alkyl and aryl polyfluroethane, l,1,2-trichloro-1,2,2-trifluoroethane, dibromosiloxanes and copolymers thereof with alkylene oxides, fluoromethane and monobromodifluoroethane. Mixtures foam-stabilising agents, for example ethyl cellulose, of these low boiling-point liquids one with another and/or colouring matters, plasticisers, for example dialkyl with other substituted or unsubstituted hydrocarbons may phthalates and flame-proofing agents, for example tris-B- also be used. Such liquids are usually employed in amounts chloroethylphosphate and tris-chloropropyl phosphate. of from 5 to 40% of the weight of polyhydroxy compound. The invention is illustrated but not limited by the fol- The preparation of the polyurethane may be carried lowing examples in which the parts are by weight. out using conventional techniques and equipment. The nickel di(hydrocarbyl) dithiophosphate or combination EXAMPLE 1 of nickel and zinc compounds may be incorporated in the T 100 parts f an oxypropylated l l f molecular reaction mixture in the form of a solution or dispersion i h approximately 3000 d h d l va1ue 56 n one of the reaction mixture ingredients, for example KOH/g. is added 0.5 part of nickel bis(acetylacetonate) the P y y y compound or the Polylsoeyemate in an and 0.5 part of zinc dinonyl dithiophosphate. To this mixiheft Solvent Such as dlmethylsulphoxlde, dlmethylfofmture is then added 4.6 parts of a solution comprising 3.5 amide 0f dhhethyleeetamldeparts of water, 1 part of a siloxaneoxyalkylene copolymer The elleet of the Said hlekel and Zinc Compounds y and 0.1 part of triethylenediamine and then 0.3 part of he further enhanced y also using other compounds- Such stannous octoate. 44.5 parts of an 80:20 mixture of tolylcompounds include Phosphltes, for example triPhenyl ene-2,4- and 2,6-diisocyanates are rapidly stirred into the Phosphlte and y -P P i y l l blend and the mixture is poured into a mould. zloetahe, yP P P for eXamPle triethylarnine The resultant foam is then compared with a control yp p p thiOPhQSPhlteS, for example lrlleuryltrlfoam of the same formulation from which the stabilisingthlOPhOSPhlte, thloethers, for example dlleurylthlodlpfeadditive has been omitted. After 4 weeks exposure to day- P Phenolic ahtlOXldahts, for example yl light the control sample is of an orange-brown hue whereeyeleheXyl)-4;6-dimethylphehol, tertiary hutyl eateehol, as that containing nickel bisracetylacetonate and zinc di- P Py gellate, y a y y nonyldithiophosphate is very pale yellow. Similar results P and 2,6"dl-tertiafy hutyl P y y hofate, are obtained after 36 hours irradiation from a mercury and light stabilisers, for example y y P lamp. Samples of the two above foams measuring apnones, 2-hydroxyphenylbenztriazoles, tx-cyanoacrylatcs proximately 3 X 1" x 1 are placed in a desiccator of and phenylsalicylates. 10" internal diameter. The desiccator is evacuated and 5 desired there y also he included in the P y ml. nitrogen dioxide gas are admitted followed immedithane-forming reaction mixture 8 cat ly Su b e ately by sufiicient air to regain atmospheric pressure withcatalysts are Well-known in the art an i clude in pa in the desiccator. The foam containing the nickel acetyl tielllaf tertiairy amlnes- Examples of Suitable tertiary acetonate and zinc dinonyldithiophosphate assumes a light amines in lud tri hyl m n m yl y brown orange hue whereas the control sample becomes a methylethanolamine, dimethylbenzylamine, dimethylh da k orange-brown, eyelehexylamine, dimethylPhehylethylamihe, yl- Results using other stabilisers as described generally 1,3-butanediamine, triethylene diamine, N-alkyl-morphoabove are tabulated below. In each case foam formulalines, N-alkylpyrrolidines, N-alkylpiperidines, N,N'-ditions of tests used are identical with those described above.

Colour of foam after- Parts by weight 36 hrs. UV irradiation Foam No. Additions used 1 weeks daylight (mercury lamp) Treatment with NO;

Control. None Light orange-brown... Light orange-brown... Dark orange-brown. 2 Ni diisopropyl dithiophosphate 0.5 V. pale-yello Colourless Light brown orange.

Zinc dinonyldithiophosphate 0. 5 3 Nickel bis(acetylacetouate) 0. 5 A most colourless "do Do.

2-(a-methylcyelohexyl) -4,6-dimethylphenol 0. 5 4 Ni dicyclohexyldithiophosphate 0.5 do ..d0 Do. 5 Ni diphenyldithiophosphate 0. 5 V. pale-yellow Almost colourless- Do. 6 Ni di(C H OCHzCHgOOHgCH )dithiophosphate 0.5 Almost colourless--. Colourless Do.

CH3 7 Ni di(OH3(OCH?&H)3)dithiophosphate 0.5 .do d0 Do. 8 Ni dinonyldithiophosphate 0.5 .do do Do. 9 4E3tlflgfillltthfittfiigtili 3:22 L no 10 4h;Slittfitlfllilithliiilifi::.- 8:32 l 11 "l5; filigfilfifilliifillfila wit;::" 3252 pale yellow 12 4%?tlittZhtttttllffiiiihfi:: 2:32

methyl 4,4 bipiperidyl and 4-dimethylaminopyridine. Amine salts such as dimethylbenzylamine lactate are also EXAMPLE 2 suitable. Other suitable catalysts include non-basic or- 2014 Parts Of a polyethylene adipate haying y y ganic compounds of metals, for example dibutyltin divalue of 54.3 mg. KOH/g. and acid value 1.62 mg. laurate, dibutyltin diacetate, stannous carboxylates such KOH/g., 1325 parts of diphenylmethane-4,4'-diisocyanate as stannous octoate and lead carboxylates such as lead and 2.0 parts of adipic acid are heated together at 80 C. acetate and lead octoate. Mixtures of catalysts are often for 1 hour and cooled to give 3339 parts of a liquid preparticularly advantageous. polymer A.

3000 parts of prepolymer A are subsequently reacted parts of a moisture-curing prepolymer derived from a at 85 C. with 317 parts of 1,4-butanediol to give a saturated polyester polyol and toluene diisocyanate in 50 liquid composition which rapidly solidifies to a brittle parts of a mixture of butyl acetate and 4-methy1-4-methwhite opaque product. This product is stoved in air at 110 oxypentan-Z-one was added 0.5 part of nickel dinonyldi- C. for 24 hours to give a tough elastomeric material of a 5 thiophosphate. The resultant solution was spread in a film light yellow colour. of thickness 0.003 inch on a glazed White tile and left to A repeat preparation of 3316 parts of the prepolymer A cure in the atmosphere for twelve hours. The cured film which contains 2.0 parts of nickel bis(ethoxyethoxyethy1) was partially masked and then exposed to a mercury lamp dithiophosphate is subsequently reacted with 350 parts of for 24 hours when it was found that both the exposed and 1,4-butanediol according to the above conditions to give a unexposed parts presented an identical appearance.

white product whose colour remains unchanged on stov- A film was similarly prepared from which the nickel ing in air at 110 C. for 24 hours. additive was omitted and subjected to the same exposure Samples of the above materials with and without stafrom the mercury lamp. The unmasked part of this film biliser are partly masked and irradiated by a mercury was found to be distinctly discoloured to a yellow shade lamp for 36 hours. The sample with stabiliser becomes a compared with the masked part which was unaffected. very pale yellow colour whereas the control sample be- What is claimed is: comes relatively a much deeper brown shade. 1. A stabilized polyurethane containing a stabilzer coin- EXAMPLE 3 prising 0.01 to 5 percent by weight of a member selected from the group consisting of (1) a nickel salt of a dithio- 100 parts of a polyester prepared by reacting 228 parts h h i id f th formula of adipic acid, 177 parts of diethylene glycol and 8.16

parts of pentaerythritol and having a hydroxyl value of 67 mg. KOH/g. and an acid value of 5 mg. KOH/g. are P mixed with 47 parts of a 65:35 mixture of tolylene-2,4- I and 2,6-diisocyanates. To this mixture is added with vigorous stirring an activator mixture consisting of 5 parts of Wherem i R each lndependenfly are selected from the Water 06 part of NNdimethYl cyclohexylamine, part group consisting of alkyl, cycloalkyl and aryl radicals havof a condensate of octylphenol with approximately 7.5 mgflp to 9 f i atoms and an alkyl Polyoxyalkylene molecular proportions of ethylene oxide, 0.2 part of the Tadlcal contalllmg P to 10 Car on atoms and up to 3 disodium Salt of sulphated polypropylene glycol (molecw oxalkylene residues and (2) a combination of a n ckel lat weight approximately 2000) and 03 part of a ,fl ketoenolate selected from the group consisting of nickel densate of castor oil fatty acids with 2.5 molecular prol (acajtylacetoneh nlckel bls (e thylacetoacet?te) p portions of ethylene oxide At the commencement of nickel bis (be izoylacetoiie), and zinc salt of said dithiofoaming the reaction mixture is poured into a mould Phosphonc f were aflexible foam is formed. 2. The stabilized polyurethane of claim wherein said Further foams are then prepared as described above but stabilizer is said nickel salt of said dithiophosphoric acid also including in the reaction mixture an anti-scorching m comblnatlon Wlth zlnc Salt of sald dlthlophosphonc agent in the proportions stated in the following table. 30- aclddiuin hypophosphite is incorporated as a solution in the 1i stabl lzed polyurethane 9 i 1 f water used in the reaction. Tertiary butyl catechol and 40 15 said {nckel Salt 9 Sald dlthlophosphonc acld nickel dinonyldithiophosphate are incorporated in the polym Combmatlon Wlth a Zmc bls (acetylacetone)' ester resin.

Pieces of foam approximately 1 inch square and 3 References Clted inches long are cut from each foam and heated in an UNITED STATES PATENTS oven at 180 C. fOI 1 110111. The table bClOW describes the 3 499 9 3/197O L i et aL 2 0 45 57 appearance of the foams after this treatment. All the 3,377,322 4/196g witsiepc 26g 77 5 foams are colourless before being heated. 3,245,923 4/1966 Manzena et 1 260 2.5 P t b 3,193,525 7/1965 Kallert et al 26045.9 a! s y 2 786 044 3/1957 Warner et al. 26045.75 X

t. A i f 185 P3122 ait.?r%f?ig1 iii 3,179,627 4/1965 Twitchett 260--45.75 Additive of resin at 180 C. N FOREIGN PATENTS Nttisaxaiaiaaiasirsrtat "arr tittiit 872 094 7/1961 G t B 5 Tert.butylcatecho1 01 Orange -bro wn. rea ntam 2 4 N1 Tert. butylcateoho1 0,05 V 1 11 77 965 Germany 2602.5 AI Ni dinonyldithiophosphatc 0.05 My pa eye 3 ggg g gggs g g 8: }Almost colourless. DONALD E. CZAJA, Primary Examiner C. W. IVY, Assistant Examiner EXAMPLE 4 To parts of a solution (having an NCO content 6 0 of 2.5% and a viscosity of 2.5 poises at 25 C.) of 50 260-25 BB, 45.7 P, 45.75 R, 45.8 N, 45.95 

